Ultraviolet light stabilized polypropylene with hydroxyanthraquinones



United States Patent 3,378,519 ULTRAVIOLET LIGHT STABILIZED POLYPROPYL- ENE WITH HYDROXYANTHRAQUINONES Gordon C. Newland and John W. Tamblyn, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation-impart of application Ser. No. 413,358, Nov. 23, 1964, which is a continuation-in-part of application Ser. No. 162,963, Dec. 28, 1961. This applicationMar. 16, 1966, Ser. No. 534,685

10 Claims. (Cl. 260-4535) ABSTRACT OF THE DISCLOSURE A normally solid thermoplastic composition comprising a poly-u-olefin'and, at a concentration suflicient to substantially inhibit ultraviolet light degradation of said poly-a-olefin, at least one substituted anthraquinone.

DISCLOSURE This patent application is a continuation-in-part of the US. patent application Ser. No. 413,358, filed Nov. 23, 1964, for Ultraviolet Light Stabilized l-olefin Resin Composition (now abandoned), which in turn was a continuation-in-part of Ser. No. 162,963, Dec. 28, 1961, now US. Patent 3,166,529, issued on Jan. 19, 1965, for Light Stabilized Poly-u-Olefin Plastic Composition.

This invention resides in the chemical arts. It pertains to l-olefin resins and to the problem of stabilizing these resins relative to the degradative effects of ultraviolet light.

Normally solid polymers of l-olefins, such as the well known normally solid polyethylene and crystalline polypropylene, are thermoplastic, synthetic resins which have gained widespread use as materials of construction. However, as is also Well known, normally solid l-olefin resins undergo a photochemical degradation when exposed to ultraviolet light. This eifect is frequently termed weathering. It appears to be a photooxidation process which causes rupture of the polymer chains and formation of carbonyl (=C=O) groups. As this degradation progresses, articles manufactured from l-olefin resins tend to crack, become brittle and lose tensile strength to the extent of mechanical failure.

This invention is based upon the discovery that certain anthraquinones confer on l-olefin resins a high degree of stability to embrittlement by action of ultraviolet light.

In summary, this invention comprises a normally solid, thermoplastic composition consisting essentially of normally solid l-olefin resin material and, at an ultraviolet light stabilizing concentration, at least one substituted anthraquinone represented by formula:

III, 0 R

s 9 1 R 7 |W4a 6 a R 10 l R R (Formula I) wherein R in each case is a radical independenfly selected from the group consisting of the hydrogen, hydroxy, nitro, C -C alkyl, halide, trifluoro, phenoxy, phenyl, C C- alkoxy, mono(C C alkyl)amino and di(C C alkyl) amino radicals, and at least one R is a radical selected from said group other than hydrogen.

Of the various substituted anthraquinones that are useful in the practice of the present invention those that are particularly preferred have the structure of Formula I, above, and have at least one hydroxy substituent on the anthraquinone nucleus. Thus, particularly preferred ultraviolet stabilizers for poly-l-olefins are the hydroxyantbraquinones encompassed by the foregoing Formula I. Still further preferred are the hydroxyanthraquinones (encompassed by Formula I, above) that contain either one or two hydroxysubstituents on the anthraquinone nucleus.

The normally solid, l-olefin resin material of this invention consists essentially of at least one, normally solid, l-olefin polymer. Such a polymer, commonly referred to generically as a poly-a-olcfin, is one which is derived from a l-monoolefinic hydrocarbon having 2-20 carbon atoms, generally 2-10 carbon atoms, preferably 2-6 carbon atoms and usually 2-4 carbon atoms. It is also provided by the normally solid copolymers, which include graft polymers, addition polymers, block polymers and the like of l-monoolefinic hydrocarbons having 2-20 carbon atoms, generally 2-10 carbon atoms, preferably2-6 carbon atoms and commonly 2-4 carbon atoms, as well as of these l-monoolefinic hydrocarbons and other compounds. Examples of a normally solid polymer derived from a l-monoolefinic hydrocarbon having 240 carbon atoms include the linear and branched, low density and high density, crystalline and amorphous, normally solid homopolymers and copolymers of ethylene, propylene, 1- butene, isob-utylene, l-pentene, Z-methyl-l-pentene, 3- methyl-l-butene, l-hexene, 3,3-dimethyl-1-butene, l-heptcne, l-octene, l-nonene, l-decene, 4-methyl-1-pentene, 4-methyl-l-hexene, S-ethyl-l-hexene, 6-methyl-l-heptene, 6-ethyl-1-heptene, styrene, allyl benzene and the like. Processes for preparing a normally solid l-olefin polymer are well known and described in detail in the prior art. See, for example, the US. Patent No. 2,153,- 553, to Fawcett et al., the US. Patent No. 2,912,429, to Cash, and the US. Patent No. 2,917,500, to Hagemeyer et al. In general, a normally solid, l-olefin resin is a thermoplastic material which at 20 C. is solid. It includes the so-called poly-a-olefin waxes which usually have average molecular weights in a range from about 3000 to about The normally solid, l-olefin resin portion of the 1- olefin composition of this invention, in addition to at least one normally solid, l-olefin resin, can also comprise other polymeric components. Thus, it can comprise a normally solid resin derived from another l-monoolefinic hydrocarbon having 2-20 carbon atoms. It can comprise a different kind of polymer, generally present as a physical property improver.

The anthraquinones of this invention, when incorporated into l-olefin resin material, function to inhibit ultraviolet light degradation of the material. Examples of these anthraquinones are:

The anthraquinones of this invention generally are readily available or can be readily synthesized. Several processes for synthesizing them are disclosed in the literature. Topic in Organic Chemistry," Fieser and Fieser, Reinhold Pub. Corp. at page 20, gives a general method for the preparation of substituted anthraquinones by the condensation of the corresponding phthalic anhydride not limited to these specific embodiments unless otherwise indicated.

Example 1 This example illustrates the synthesis of 1,6-diphenoxyand the corresponding phenol. A general process of synthesis is given by M. S. Newman, J. Amer. Chem. Soc. gg 1 6 h d 1942, 64, 23, 24. A synthesis of 6,8-diphenyl-1,4-di- 558 if raqumone are 'f hydroxyanthraquinone is described in Bull. Soc. Chim. 3 ggams o P am 23 grams of Potassium b France (1963) (6), 1141-5. Syntheses of alizarin com- 2 grams of copper The sulting mixture is boiled ently for 3 /2 hours under an air conpounds are described in W. H. Perkins, J. Chem. Soc. d r o 1891 59 1012 and s. D. Ross and M. Schwarz J. Amer. The i cqded. to 80 ES chenl Soc 1955, 77 3020. 130 grams of sodium hydroxide in 1300 milliliters of Concentration of the ultraviolet light inhibitor of this g g g if h g f 531 hg T l invention in the normally solid plastic composition is at boiled 200 ,5 g3 H? least sufficient to substantially inhibit ultraviolet light deg- 1 d d m1 hers o ano are l en radation of the l-olefin resin material. Any concentrame I T 6 product i obtame? conslsts essmlany of 1,6-diphenoxyanthraquinone. This can be verified by a non greater than this depends generally upon the extent carbon and h dro en anal Sis Cale 627 of ultraviolet light stabilization desired. This in turn de- 4 087 t i 'i pends upon a number of factors including subsequent ypl a n environmental conditions to which the plastic composi- Exam 1 2 p e tion of this invention is intended to be exposed. In general, however, a concentration of the ultraviolet light sta- P Illustrates the syhihesls 0f Y y' bilizer of this invention in a range from about 0.1 to 4:Sdmliroamhraqumohfi about 10% by weight of the total l-olefin resin content 320 grams of u u tc acid are added to a mixof the composition, that is, the l-olefin resin material, ture of 39 grams hlmmg Illtflc acid and 101 gives satisfactory results in most end uses of the comgrams 0f 100% shlfllrlc a 36 g ams Of 1,6-diphenoxyposition anthraquinone are added portionwise t0 the mixture of The normally solid, l-olefin resin composition of t acids at atemperature below C. The reaction mixture invention can also compriss other additives Such as f r thus obtained is stirred for 16 hours at room temperature example, antioxidants, thermal stabilizers, anticorrosion 30 and then 2 hours at The resclioh mixture is then additives, antistatic agents, foaming agents, plasticizers, Poured into 11/2 liters of Water, filtered and Pressed colorants uch as dyes and pigments vaxes mold relief The filter cake iS then added to grams Of sodium agents, slip agents, antiblocking agents, fillers, extenders, hydroxide in 1250 milliliters of Water at C: Cooled and the like, including physical property improvers other to h 15 hours, Washed with than polymeric compounds water and again stirred in 300 milliliters of water made The normally solid, l-olefin resin composition of this i to Congo red paper i concentrated hydrochloric invention is made by incorporating the ultraviolet light acid. The slurry is stirred for 1 hour, filtered and then Stabilizer f this ihvgntion into the normally Solid 1 1 washed until neutral. The solids thus obtained are dried fin resin material. Generally, such incorporation is perand then recrysh'llhled m chlorohehlehe to give a formed by any one of a number of known methods, such 40 profjuct that Qohslsts essehhahy 0f s y yi as, for example, roll compounding, extrusion, solv t dinitroanthraquinone. This can be confirmed by a carbon, mixing and the like. For instance, such incorporation hydrogen and hiifogfih ahalysis- Cale-I H: can be performed by heating or otherwise softening the 132%, yp fihdihgl C:48-74%; H: normally solid resin material to a workable consistency 153%, and then workirig in, as by roll compounding, the ultra- Example 3 violet light stabilizer of this invention until a substantialy uniform blend dispersion is Obtained- Generally, This example illustrates the synthesis of 2-t-butyl-l,4- such incorporation takes place at the same time that other dih d mh i additives are normally incorporated into the l-olefin resin 3,19 grams f Lb -1 4 dih d h i material and usually along with such other additives as 15 milliliters of t-butylamine and 200 milliliters of ethylthe formulation Of thfi particular embodiment Of the plaseng glycol monomethyl ether are admixed The resulting tic composition q mixture is heated slowly to reflux and then refluxed for The normally solid Pldstic Composition of this 20 hours. The reaction mixture thus obtained is cooled tion is useful in coatings and as a material of construc- H to room temperature, filt d Washed i h Water d tion for shaped articles Thus, the composition can be do dried to give a product consisting essentially of Z-t-butylmade into various shaped articles such as, for example, 1 4- i h i A typical yield f the prodpellets, sheeting, films, bars, tubes, filaments, fibers, spenet i 238 granm cially shaped structural elements and the like as by conventional casting and molding techniques which include Examplc 4-8 extrusion, blow molding and the like. 60 These examples illustrate specific embodiments of a This invention is further illustrated by the following polyethylene composition of this invention. examples of various aspects thereof, including preferred The formulations of these embodiments are set forth specific embodiments of this invention. This invention is in decreasing order of preference in the following table.

Concentration in Parts by Wt. Components Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex.

Normally solid polyethylene 100 100 100 10 1,5-dihydroxy-4-dodccyloxy-iimitroanthraquinone 1 1-hydroxy-8-i1itroanthraquinone- 1,5-dihydroxy-4,8-dinitroantliraquinorlo 1,5 dihydroxyanthraquinone 1,S-dihydroxyanthraquinone.

3,378,519 .5 6 The specific embodiments according to these formula The formulations of these embodiments are set forth in trons are made by hot roll-compounding the normally decreasing order of preference in the following table.

Concentrations in Parts by Wt.

Components Ex. 25 Ex. 26 Ex. 27 Ex. 28

Normally solid poly(1-oetadecene) 100 100 100 100 1-hydroxy-8-nitroanthraqninnnp 5 1,5-dihydroxy-4,8-dinitroanthraquinone 5 1,5-dihydroxyanthraquinone. 5

1,8-dihydroxyanthraquinone 5 solid polyethylene with the other component called for in The specific embodiments according to these formulaeach formulation. The specific embodiments thus made tions are made by dry blending the components called for are obtained in the form of roll slabs. in each formulation.

These specific embodiments are useful in films, coatings The specific compositions thus obtained are useful in and in the fabrication of shaped articles. films, coatings and in the fabrication of shaped articles. Examples 9-24 Examples 29-31 These examples illustrate specific embodiments of a 20 These examples illustrate specific embodiments of a polypropylene composition of this invention. poly(3-methyl-1-butene) composition of this invention.

The formulations of these specific embodiments are The formulations of these specific embodiments are presented in decreasing order of preference in the followpresented in decreasing order of preference in the following table. ing table.

Concentrations in Parts by Weight Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 9 10 ll 12 13 14 15 16 17 18 19 20 21 22 23 24 Crystalline polypropylene.-- 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Dilauryl 3,3-thiodipropionat 8 0- 8 4,4-butylidenebis (fi-t-butyl-n 0. 4 l'hydroxy-8Fnitroanthraquinone l 5 1,7-dihydroxy-4,8-dinitroanthraquinono l-hydroxy-S-nitroanthraquinone 1,5'dil1ydroXy-4,S-dinitroanthraquinone 2-t-butylamino-1,4-dihydroxy-anthraquinone 1,6-dihydroxy-4,5-dinitr0anthraquinone 1,6-diphenoxyanthraquinone l,5-din.itro2,6-dihydroxyanthraquinone l,8-dihydroxyanthraquinone 1,4-dihydroxyanthraquinone. 1,5-dihydroxyanthraqulnone. l-hydroxyanthraquinone 1,8-dihydroxy-2,4,5,7-tetrabromoanthraqu1none 5 1,4-dihydroxy-2- (2-hydroxyethyl) -anthraquinone 5 Components The specific embodiments according to these formulations are made by admixing the polypropylene with the Concentrations in Parts 0 Components by Wt. other component or components called ior 1n eachformulation. Such admixing can be performed in Warm Ex. 29 Ex.30 Ex. 31 (145 C.) tetralm with the polypropylene being com- Normally Solid polygmethyhbbgtene) 100 100 100 pletely dissolved therein at a weight ratio of 1 part of ,gfi gyg xy t, i hmtroanthraqumone 5 p p py to 25 parts of tetralin- In such case the 1inlhdrfigilltfiiigfilfigfiijjjjj;:jj; jj:jjjjj suiting dope is generally cast and the tetralin evaporated to leave a film of the polypropylene composition.

The specific embodiments according to these formula- The specific embodiments according to these formulations are also made by dry blending polypropylene pellets tions are made by dry blending the components called for in which other additives such as 4,4-butylidenebis(6-tin each formulation. butyl-m-cresol) and dilauryl 3,3'-thi0dipropionate are The specific compositions thus obtained are useful in added prior to formation of the pellets. films, coatings, and in the fabrication of shaped articles.

The specific compositions thus obtained are useful in films, coatings, fibers and in the fabrication of shaped Examples 32 35 articles.

These examples illustrate specific embodiments of a poly(4-methyl-1-pentene) composition of this invention. The formulations of these specific embodiments are Examples 2528 These examples illustrate specific embodiments of a presented in decreasing order of preference in the followp0ly(1-octadecene) composition of this invention. ing table.

Concentrations in Parts by Wt. Components EX. 32 EX. 33 EX. 34 EX. 35

Normally solid po1y(4-methyl-1-peutene) 100 100 100 l-hydroxy-B-nltroanthraqninnnp 5 1,5-dihydroxy-4,8-dinitroanthmquinone 5 1,5-dihydroxyanthraquinone 5 1,8-dihydroxyanthraquinone 5 The specific embodiments according to these formulations are made by dry blending the components called for in each formulation.

The specific compositions thus obtained are useful in films, coatings and in the fabrication of shaped articles.

Examples 3 6-3 8 Concentrations in Parts by Components Wt.

Ex. 37 Ex. 38

Normally solid eopolymer of propylene and l-butene at weight ratio of propylene to l-buteue of 80:20

1,5-dihydroxy-4,8-dinitroantl1raquinon 1,B-dihydroxyanthraquinone 1,5-dihydroxyanthraqninone The specific embodiments according to these formulations are made by dry blending the components call for in each formulation.

The specific composition thus obtained are useful in films, coatings and in the fabrication of shaped articles.

The ultraviolet light stability of the l-olefin resin composition of this invention is demonstrated by the following data obtained at various times in the ultraviolet light stability testing of samples of various l-olefin resin compositions.

The first series of tests involved samples of polyethylene compositions. The samples were made from a normally solid polyethylene having a density of 0.92. Each sample was made by hot roll compounding the polyethylene and 1 part per 100 parts of polyethylene of the additive indicated for that sample in the following table, the temperature of the rear roll being at 220 F. and the temperature of the front roll being at 270 F. The total milling time for each sample was 4 minutes. Flat plates, 0.048 inch thick, were compression molded from the samples. The stability testing comprised exposing these fiat plates outdoors at Kingsport, Tenn, for 60 days. At the end of that time the relative carbonyl content of the exposed plates was determined by infrared absorption at 5.82 4.

The formulations of the samples and the test results are summarized in the following table.

1,8-dihydroxyanthraquinone Samples 26, it will be observed, correspond to the formulations of Examples 4-8.

These data show that the specific anthraquinones of this invention involved in this series of tests were effective ultraviolet light stabilizers for polyethylene.

The next series of tests comprised samples of polypropylene compositions. Each sample in this series was made by preparing a 4% dope of a crystalline polypropylene and tetralin and in each case adding 5 parts by weight of the additive indicated for that sample in the following table to 100 parts by weight of the crystalline polypropylene contained in the dope. After heating the resulting sample at 145 C. for 40 minutes, it was cast onto a ferro-type plate which was established and maintained at a temperature of 143 C. After evaporation of the tetralin from the cast dope, which require about minutes at 143 C., the plate and resulting film were quenched in water and the film peeled from the plate. Test specimens (2.5 inches x 0.5 inch) were cut from these films and exposed in an Atlas Twin-Arc Weather-Ometer, type DLTS, modified with ten 20 watt Westinghouse fluorescent sunlamps [Anal. Chem, 25, 460 (1953)], which apparatus is hereinafter referred to as the modified Weather-Ometer. Test results in the modified Weather- Ometer have been found to correlate with test results obtained outdoors at Kingsport, Tenn. The exposure time required to render the film specimens brittle when creased with the exposed side of the film on the outside of the crease was thereby determined. From the exposure times for each specimen, one of which was a film of crystalline polypropylene containing no ultraviolet light inhibitor, a stabilization rating was calculated for each sample. The stabilization rating is the ratio of exposure time required to embrittle the film with an ultraviolet light inhibitor to the exposure time required to emprittle the film without an altraviolet light inhibitor. The formulations of the samples and results of the stability testing are summarized in the following table.

Stabilization Rating Additive none. 1,fidiliydroxy4,5-dinitroanthraqulnone 1,6-dlphenoxyanthraquinone 1,5-dlnitro-Z,e-dihydroxyanthraquinone. 1,8-dihydroxyanthraqulnone 1,4-dlhydroxyauthraquinone l,5-dihydroxysnthraquinone 13. l-hydroxyanthraquinone 14 1,8-dihydroxy-2,4,5,7-tetrabromoanthra- N terminus-$005 qulnone. l5 1,4-dihydroxy-2-(2-hydroxyethyl)-anthraquinone.

Samples 2-15 correspond to the specific embodiments of Examples 10-12 and 14-24, respectively.

The stability data of the table show that the anthraquinone compound of this invention are effective ultraviolet light stabilizers for polypropylene.

In the next test series samples of polypropylene compositions were prepared by dry blending crystalline polypropylene pellets with the additives indicated in the following table as additional additives. The polypropylene pellets contained 4,4'-butylidenebis(6-t-butyl-m-cres0l) at a concentration of 0.4% by weight based on the polypropylene and dilauryl 3,3'-thiodipropionate at a concentration of 0.8% based on the weight of the polypropylene. The concentration of each of the additional additives was 1 part per parts of crystalline polypropylene. The blended pellets of each sample were extruded as 400 denier monofilament. The monofilament specimens of each sample were then exposed in an Atlas Sunshine Arc Weather-Ometer, type XWR, and the progress of weathering was followed by periodically measuring the tenacity and elongation of the monofilament specimens. The number of hours of exposure of each specimen required to reach a 50% reduction in tenacity and elongation is thereby determined. The formulations of the samples and the results of the weathering tests are presented in the following table.

Hours of Ex osure Re- Samples 2 and 3 correspond in formulation to the specific embodiments of Examples 9 and 13, respectively.

These data show that the anthraquinones of this invention are effective ultraviolet light inhibitors in polypropylene fiber.

The next test series involved samples of normally solid poly(1-octadecene). The samples were made by dry blending poly(l-octadecene) with the additives indicated in the following table. The additives were incorporated into 10 in formulation to the specific embodiments of Examples 32-35 while samples ll-13 correspond in formulation to the specific embodiments of Examples 36-38.

These data show that the anthraquinones of this inthe poly(l-octadecene) at concentrations of based on 5 vention are effective ultraviolet light stabilizers for other the weight of the resin. The samples thus obtained were l-olefin resins. extruded at 70 C. ontoa chilled roll as mil thick Other features, advantaggs and embodiments of this films. The films were placed into the modified Weatherinvention will be apparent to those in the exercise of Ometer and the hours of exposure until embrittlement ordinary skill in the art after reading the foregoing diswas detected were determined. The test results as well 10 closures. In this regard, While specific embodiments of as formulations of the samples are presented in the this invention have been described in considerable detail, following table. variations and modifications of these embodiments can be effected within the spirit and scope of this invention as 31 mditm disclosed and claimed.

' i i0: What is claimed is:

Emblimemmlt 1. A normally .solid thermoplastic composition com- 1 None 160 prising (A) a normally solid polypropylene and (B) at 5:: 'iIiiiiiglil'ifi if iiilitftflfifitsiian:11 i338 least we W anthmquifione selected 4 1,S-dihydroxyanthmquinone 830 group consisting of 2,4,5,7-tetrabromo-l,8-d1hydroxy- 5 11841111Ydmxyanthmquinone anthraquinone, lhydroxyanthraquinone, 1,5-dihydroxy-4,

8-dinitroanthraquinone, l,4-dihydroxyanthraquin-one, 1,8- Samples 2-5 correspond in formulation to the specific dihydmxyamhfaquinone, 1,5 dihydPOXyanthfaquinone, b dim t of Examples -28, 2,6 dihydroxy-l,S-dinitroanthraquinone, 1 hydroxy-S- These data show that the anthraquinones of this invennitmanthl'aqllin'onei Y Y* q tion are effective ultraviolet light stabilizers for poly(ldiphenflXyanthraquinone, 1,7-dihYd1'0XY-4,s-dinitfoanthraoctadecene), quinone, and l,6-dihydroxy-4,S-dinitroanthraquinone, said The next series of tests comprised samples of other Substituted anthfaquinofie being Present a Concentra- 1-0lefin resins, The additives to be tested were added at liOn sufficient 1J0 substantially inhibit ultraviolet light dea 5% concentration level to a 4% by weight dope of the gradation said p yP py l-clcfiii resin in tetralin and mixed 1 hour at a tempera- A composition as in claim 1, wherein the amount ture of 145 C. The dope containing the additive in each of said substituted anthraquinone in said composition is case was cast on a ferro-type plate at a tem ratur of from about 0.1 to about 10 weight percent, based on the 143 C. and the tetralin was evaporated. When the tetralin Weight 0f Said P yp py was completely evaporated the film remaining on the 3. Aoomposition as in claim 1, wherein said substituted plate, which film was about 0.003 inch thick, was anthraquinone i y yq quenched in cold water and peeled from the plate, Te t 4. A composition as in claim 1, wherein .said substituted specimens of the film in each case (2.5 inches x 0.5 inch) anthraquinooe is 1fi-dihYdP0XY-4,idifinfoanthraquinfinewere cut from these films and exposed in the modified 5. Aoompositionas in claim 1, wherein said substituted Weather-Ometer and the specimen observed for the onset anthraquinone is 1-hydroxy-S-nitroanthraquinone. of embrittlement. The hours required for embrittlement 4O 6. A composition as in claim 1, wherein said substituted and the stabilization rating of each sample was thereby anthraquinone is 1,7-dihydroxy-4,S-dinitroanthraquinone. determined. The exposure times to reach embrittlernent, 7. A composition as in claim 1, wherein said substituted stabilization ratings and the formulations of the samples anthraquinone is 1,5-dihydr-oxy-4,S-dinitroanthraquinone. are presented in the following table. In this connection the 8. A composition as in claim 1, wherein said substituted copolymer of propylene and l-butene referred to in the anthraquinone is l,S-dihydroxyanthraquinone. table had a weight ratio of propylene to l-butene of 9.Acomposition as in claim 1, wherein said substituted :20. anthraquinone is 1,8-dihydroxyanthraquinone.

Sample 1-O1efin Resin Hours of Stabilization N 0. Exposure Rating 1 Normally solid poly(3-rnethyl-1-butene) None 19 1.0 2 do 1,5-dihydroxy-4,8din.itro-anthraquinon 114 6. 0 '1 do 1,5-dihydroxyanthraquinone 96 5. 0 4 do 1,8-dihydroxyanthraquinone- 72 3. 8 5 Normally solid poly(4-methy1-1-pentene) None 16 1.0 6 do l-hydroxy-S-nitroanthraquinone 230 14. 4 7 dn 1,5dlhydroxy-4,8-dinitroanthraquinone 96 6.0 8 do 1,5-dihydroxyanthraquinone 72 4.5 1 do 1,8-dihydroxyanthraquinoue- 64 4. 0 10 Normally solid copolymer of propylene and N one 22 1. 0 1 l-butene' do 1,5-dihydroxy-4,8-din.itroanthraqu1none 440 20.0 12 do 1,8-dihydroxyanthraquinone- 380 17. 0 13 do 1,5-dihydroxyanthraquinone- 232 14. 0

Samples 2-4 correspond in formulation to the specific embodiments of Examples 29-31, samples 69 correspond 10. A shaped article of claim 1.

the composition defined in References Cited UNITED STATES PATENTS DONALD 'E. CZAJA, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

H. E. TAYLOR, JR., Assistant Examiner. 

